• Title/Summary/Keyword: Excited state

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Theoretical Investigation of 2,3-bis(2,4,5-trimethyl-3-thienyl)maleic anhydride: A Thermally Irreversible Photochromic System

  • 조한국;정병서
    • Bulletin of the Korean Chemical Society
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    • v.19 no.3
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    • pp.308-313
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    • 1998
  • A thermally irreversible photochromic system, 2,3-bis(2,4,5-trimethyl-3-thienyl)maleic anhydride (MTMA), has been studied by semi-empirical molecular orbital methods. There are one pair of stable conformations for the closed-ring form and three pairs for the open-ring form, each pair consisting of two mirror-image conformations. Interconversion between the parallel and anti-parallel conformations of the open-ring form is restricted due to high energy barriers. Only the anti-parallel conformation appears to be responsible for photochromic cyclization. Thermostability of the compound is attributed to an avoided crossing at high energy in the ground states of the isomers, whereas the photoreactivity can be explained by the mutually connected excited singlet (S1) states of the isomers, forming a double well potential with a low energy barrier. The large solvent effects can be partly explained with the low dipole moment of the anti-parallel conformation of MTMA in the S1 state. The large variation of quantum efficiency suggests that excess vibronic energy can be utilized to provide the activation energy for the photochromic reaction.

Photophysical properties of Khellin

  • Shim, Sang-Chul;Kang, Ho-Kwon
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.341-344
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    • 1987
  • The fluorescence quantum yield of khellin is sensitive to temperature and to the nature of solvents, especially the proton-donating ability in solute-to-solvent hydrogen bonding. The intersystem crossing quantum yields are 0.4 and 0.15 in acetonitrile and ethanol, respectively. The fluorescence quantum yields in ethanol and isopentane at 77 K are 0.61 and 0.07, respectively, both of which are much larger than the values at room temperature. The phosphorescence lifetime is relatively long and decreases with decreasing solvent polarity. The phosphorescence to fluorescence quantum yield ratio is very small and remains unchanged in various solvents. The results suggest that internal conversion is an important decay channel of the excited singlet state of khellin, especially in the hydrogen-bonding hydroxyl solvents.

Solvent Dependence of Absorption and Fluorescence Spectra of Piroxicam. A Possible Intramolecular Proton Transfer in the Excited State

  • Yoon, Min-Joong;Choi, Hyong-Nae;Kwon, Hwang-Won;Park, Koon-Ha
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.171-175
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    • 1988
  • The spectral properties of piroxicam in different solvents are similar to those of its skeletal precursor, HMBDC. The maximum absorption and emission wavelengths strongly depend on the hydrogen bonding ability of the solvent, and it is shown that intramolecular hydrogen bonding between the -OH and the ortho carbonyl group of the parent benzothiazine ring plays an important role in the solvent-dependence of their spectroscopic properties. The fluorescence spectra in aprotic nonpolar solvent exhibit abnormally large Stokes-shifted (${\sim}9,000cm^{-1}$) emission bands in contrast to the spectra in water. In ethanol, dual emission bands with two different fractional components of lifetimes have been observed. These results suggest that the abnormally red-shifted emission is attributed to the proton transferred form of an intramolecularly hydrogen-bonded closed conformer.

Formation of a Stationary Light Pulse in a Doppler-Broadened EIT Medium

  • Chough, Y.T.
    • Journal of the Korean Physical Society
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    • v.73 no.10
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    • pp.1479-1485
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    • 2018
  • A number of experiments have been performed on light slowing and stopping in the electromagnetically induced transparency (EIT) media of hot atomic gases where the Doppler-shift may add detunings to the field frequencies in an inhomogeneous fashion. We provide here a theoretical analysis as to the effect of such a Doppler-broadened environment on the dynamics of the system in comparison to a cold atomic medium. We will show that one of the most critical factors in the formation of a stationary light pulse is the enhancement of the excited-state decay rate caused by the collisions between the atoms of the medium and the molecules of the buffer gas.

Measurement of Spatiotemporal Distribution for the Density of Excited Xe Atoms in the 1s5 in Accordance with Various ITO-shapes in Ac-PDP (교류형 플라즈마 평판 표시장치(AC-PDP)에서 ITO 전극 구조에 따른 Xe 여기종의 시공간 밀도 분포 연구)

  • Cho, S.H.;Hong, Y.J.;Son, C.G.;Han, Y.G.;Jeong, Y.H.;Gwon, G.C.;Hong, B.H.;Cho, G.S.;Choi, E.H.
    • Journal of the Korean Vacuum Society
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    • v.18 no.1
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    • pp.54-59
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    • 2009
  • We have measured the spatiotemporal behavior for the density of excited Xe atoms in the $1s_5$ metastable states by laser absorption spectroscopy in accordance with various shapes of ITO electrode. The maximum density of excited Xe atoms in the Is5 state in a discharge cell for fish-boned, T-shaped and squared ITO electrodes has been measured to be $3.01{\times}10^{13}\;cm^{-3}$, $2.66{\times}10^{13}\;cm^{-3}$ and $2.06{\times}10^{13}\;cm^{-3}$, respectively. Throughout this experiment, we could understand the influence of the shapes of ITO electrode of micro discharge cell on the high efficiency of AC-PDPs.

Tunable doping sites and the impacts in photocatalysis of W-N codoped anatase TiO2

  • Choe, Hui-Chae;Sin, Dong-Bin;Yeo, Byeong-Cheol;Song, Tae-Seop;Han, Sang-Su;Park, No-Jeong;Kim, Seung-Cheol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.246-246
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    • 2016
  • Tungsten-nitrogen (W-N) co-doping has been known to enhance the photocatalytic activity of anatase titania nanoparticles by utilizing visible light. The doping effects are, however, largely dependent on calcination or annealing conditions, and thus, the massive production of quality-controlled photocatalysts still remains a challenge. Using density functional theory (DFT) thermodynamics and time-dependent DFT (TDDFT) computations, we investigate the atomic structures of N doping and W-N co-doping in anatase titania, as well as the effect of the thermal processing conditions. We find that W and N dopants predominantly constitute two complex structures: an N interstitial site near a Ti vacancy in the triple charge state and the simultaneous substitutions of Ti by W and the nearest O by N. The latter case induces highly localized shallow in-gap levels near the conduction band minimum (CBM) and the valence band maximum (VBM), whereas the defect complex yielded deep levels (1.9 eV above the VBM). Electronic structures suggest that substitutions of Ti by W and the nearest O by N improves the photocatalytic activity of anatase by band gap narrowing, while defective structure degrades the activity by an in-gap state-assisted electron-hole recombination, which explains the experimentally observed deep level-related photon absorption. Through the real-time propagation of TDDFT (rtp-TDDFT), we demonstrate that the presence of defective structure attracts excited electrons from the conduction band to a localized in-gap state within a much shorter time than the flat band lifetime of titania. Based on these results, we suggest that calcination under N-rich and O-poor conditions is desirable to eliminate the deep-level states to improve photocatalysis.

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Reaction Pattern Influenced by Relative Values in the Evaluation of Preference for Image (이미지에 대한 선호도 평가에 있어 상대가치 작용 반응 패턴)

  • Heo, Seong-Cheol
    • Science of Emotion and Sensibility
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    • v.17 no.4
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    • pp.41-50
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    • 2014
  • This study examined the characteristics of brain's reaction pattern concerning the preference for product images and compared them with the result of subjects' intuitive evaluation of their preference for the same materials. Two tests were conducted; the first one that calculated comfort properties based on brainwave measurements in order to examine the impression given by the images of products presented separately, one-by-one, and the second one that had subjects evaluate the preference directly by comparing the images of all products simultaneously. The first test was titled 'Independent Cognitive Response' and the second test, 'Relative Cognitive Response', and their characteristics were as follows. In the 'Independent Cognitive Response', the state of emotion was expressed in absolute values based on the comparison with the information accumulated through the subject's own experience and the feeling expressed as 'pleasant' or 'unpleasant' persisted as absolute values. In the 'Relative Cognitive Response', the state of emotion relative to the information of other images compared in the stage of perceiving the images was expressed, and in this case, the state of emotion described as 'calm' or 'excited' acted as relative values.

Determination of Trace Lead by Laser Resonance Ionization Spectroscopy (I). Dependence of Detection Limit on Ionization Schemes (레이저 공명이온화에 의한 극미량 납의 정량 (I). 이온화 경로에 따른 검출한계의 변화)

  • Kyuseok Song;Jong Hun Lee;Jongmin Lee
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.832-839
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    • 1992
  • Lead has been determined by Resonance Ionization Mass Spectrometry (RIMS) through one-color-two-photon ionization, two-color-two-photon ionization and three-color-three-photon ionization in a vacuum chamber equipped with Time-of-Flight(TOF) mass spectrometer. In all cases, the first excited state chosen was 6p7s($^3P_1$) state and the transition was at 283.3 nm in wavelength from the ground state. By using various concentrations of lead standard solutions, the calibration curve is obtained in the range of 0.1 ${\mu}g$ to 1.0 pg in both ionization schemes. The detection limit was estimated as 20 pg for the two-color ionization, while 10 pg for the three-color ionization experiment.

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The Effect of Incoherent Pumping in Electromagnetically Induced Absorption (전자기 유도 흡수에서의 비결맞음 펌핑 효과)

  • Moon, Han-Sub;Kim, Sook-Yung;Kim, Kyung-Dae;Lee, Chung-Hee;Lee, Rim;Kim, Haeng-Hwa;Kim, Joong-Bok
    • Korean Journal of Optics and Photonics
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    • v.13 no.5
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    • pp.449-454
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    • 2002
  • We have studied the effects of incoherent pumping on EIA at the transition between the $F_g=2$ ground state and the $F_e=3$ excited state in $^{85}Rb\;D_1$-line. Generally, the studies about EIA have been done in the cycling transition, where the population has no loss to other states. In the case of EIA by using the $^{85}Rb\;D_1$ transition line, the population is transferred to the other hyperfine state due to optical pumping. We incoherently pumped the atoms from $F_g=3\;to\;F_g=2$ with the pumping beam, which is resonant at the transition from $F_g=3\;to\;F_g=2$. We were able to observe the effects of incoherent pumping depending on the power and the polarization of the pumping beam.

Optical Properties of CaYAlO4:Tb3+/Eu3+/Ce3+ Phosphors (CaYAlO4:Tb3+/Eu3+/Ce3+형광체의 광학적 특성 분석)

  • Kang, Taewook;Ryu, Jongho;Kim, Jongsu;Kim, Gwang Chul
    • Journal of the Semiconductor & Display Technology
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    • v.16 no.4
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    • pp.86-90
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    • 2017
  • $Tb^{3+}$ or $Eu^{3+}$ or $Ce^{3+}$-doped $CaYAlO_4$ phosphor were synthesized by solid-state method. $CaYAlO_4:Tb^{3+}$ is shown that the $Tb^{3+}$-doping concentration has a significant effect on the $^5D_4/^5D_3{\rightarrow}7F_J$ (J=6,...,0) emission intensity of $Tb^{3+}$. The $CaYAlO_4:Tb^{3+}$ phosphors show tunable photoluminescence from blue to yellow with the change of doping concentration of $Tb^{3+}$ ions. The $CaYAlO_4:Eu^{3+}$ phosphors exhibit a red-orange emission of $Eu^{3+}$ corresponding to $^5D_0$, $_{1,2}{\rightarrow}^7F_J$ (J=4,...,0) transitions. The $CaYAlO_4:Ce^{3+}$ phosphors show a blue emission due to $Ce^{3+}$ ions transitions from the 5d excited state to the $^2F_{5/2}$ and $^2F_{7/2}$ ground states. The decay time of $CaYAlO_4:Tb^{3+}$ phosphors decrease from 1.33 ms to 0.97 ms as $Tb^{3+}$ concentration increases from 0.1 mol% to 7 mol%. The decay time of $CaYAlO_4:Eu^{3+}$ phosphors increase from 0.94 ms to 1.17 ms as $Eu^{3+}$ concentration increases from 1 mol% to 9 mol%.

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